EP0889029A2 - Process for the preparation of 3- (methylthio) propanal - Google Patents
Process for the preparation of 3- (methylthio) propanal Download PDFInfo
- Publication number
- EP0889029A2 EP0889029A2 EP98114518A EP98114518A EP0889029A2 EP 0889029 A2 EP0889029 A2 EP 0889029A2 EP 98114518 A EP98114518 A EP 98114518A EP 98114518 A EP98114518 A EP 98114518A EP 0889029 A2 EP0889029 A2 EP 0889029A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- acrolein
- gas
- liquid
- reaction
- methylthio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 48
- CLUWOWRTHNNBBU-UHFFFAOYSA-N 3-methylthiopropanal Chemical compound CSCCC=O CLUWOWRTHNNBBU-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims abstract description 380
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 116
- 239000007788 liquid Substances 0.000 claims abstract description 103
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- 239000000047 product Substances 0.000 claims abstract description 40
- 239000012429 reaction media Substances 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 3
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims 2
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 claims 1
- 239000007789 gas Substances 0.000 description 164
- 239000007791 liquid phase Substances 0.000 description 37
- 238000012546 transfer Methods 0.000 description 31
- 239000012071 phase Substances 0.000 description 30
- 239000000203 mixture Substances 0.000 description 18
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 16
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 16
- 239000000376 reactant Substances 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 12
- 239000006096 absorbing agent Substances 0.000 description 11
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 10
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 10
- 238000009833 condensation Methods 0.000 description 10
- 230000005494 condensation Effects 0.000 description 10
- 239000012535 impurity Substances 0.000 description 10
- 238000011084 recovery Methods 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
- KQEIJFWAXDQUPR-UHFFFAOYSA-N 2,4-diaminophenol;hydron;dichloride Chemical compound Cl.Cl.NC1=CC=C(O)C(N)=C1 KQEIJFWAXDQUPR-UHFFFAOYSA-N 0.000 description 5
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 5
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 229930182817 methionine Natural products 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- 230000003134 recirculating effect Effects 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 230000005514 two-phase flow Effects 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- -1 organic acid salt Chemical class 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- GAPYKZAARZMMGP-UHFFFAOYSA-N pyridin-1-ium;acetate Chemical compound CC(O)=O.C1=CC=NC=C1 GAPYKZAARZMMGP-UHFFFAOYSA-N 0.000 description 3
- 238000005057 refrigeration Methods 0.000 description 3
- AKXKFZDCRYJKTF-UHFFFAOYSA-N 3-Hydroxypropionaldehyde Chemical compound OCCC=O AKXKFZDCRYJKTF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000010960 commercial process Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 239000012809 cooling fluid Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- ONFOSYPQQXJWGS-UHFFFAOYSA-N 2-hydroxy-4-(methylthio)butanoic acid Chemical compound CSCCC(O)C(O)=O ONFOSYPQQXJWGS-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003797 essential amino acid Substances 0.000 description 1
- 235000020776 essential amino acid Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000013529 heat transfer fluid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- FFEARJCKVFRZRR-UHFFFAOYSA-N methionine Chemical compound CSCCC(N)C(O)=O FFEARJCKVFRZRR-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/18—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by addition of thiols to unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/783—Separation; Purification; Stabilisation; Use of additives by gas-liquid treatment, e.g. by gas-liquid absorption
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00716—Means for reactor start-up
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
EXPERIMENTAL RESULTS ON THE EFFECTS OF OPERATING VARIABLES | ||||||||||||
VARIABLES | RESULTS | |||||||||||
RUN NO. | VG (F/S) | [M/S] | YA (M%) | T (C) | CC (W%) | TR (HR) | A/M (RATIO) | PR (G/M) | REC (%) | YIELD (%) | CA (W%) | CM (W%) |
041684 (TYPICAL) | 1.30 | 0.3962 | 16.1 | 41 | .47 | 5.0 | 0.97 | 2.27 | 94.2 | 92.3 | 0.51 | 1.34 |
010984A | 1.02 | 0.3109 | 19.5 | 39 | 0.4 | 5.7 | 0.63 | 2.34 | 91.2 | 82.9 | .051 | 8.85 |
011984B | 1.13 | 0.3444 | 33.6 | 46 | 0.4 | 5.0 | 1.25 | 2.77 | 74.7 | 71.1 | 4.35 | 0.20 |
042584 | 1.76 | 0.5364 | 18.1 | 55 | 0.4 | 3.1 | 1.01 | 2.94 | 85.4 | 83.9 | 1.30 | 0.28 |
050284 | 1.68 | 0.5121 | 19.4 | 50 | 0.7 | 2.9 | 1.00 | 3.13 | 89.5 | 88.0 | 0.05 | 1.60 |
061384B | 1.44 | 0.4389 | 20.7 | 40 | .39 | 5.0 | 1.26 | 2.54 | 88.1 | 85.5 | 2.43 | 0.43 |
061384A | 1.40 | 0.4267 | 16.6 | 41 | .32 | 6.1 | 1.07 | 2.11 | 87.4 | 86.5 | .158 | .913 |
052384 | 1.45 | 0.4420 | 9.24 | 40 | .43 | 12.8 | 1.17 | 1.03 | 76.3 | 75.3 | .775 | .487 |
061484B | 1.23 | 0.3749 | 7.23 | 39 | .39 | 17.9 | 1.23 | 0.66 | 75.9 | 74.8 | 1.12 | .291 |
VG = SUPERFICIAL GAS VELOCITY,FT/SEC YA = INLET ACROLEIN CONC., MOLE % T = REACTOR TEMPEATURE DEG. C CC = CATALYST (PYRIDINE ACETATE) CONC., WT. % TR = RESIDENCE TIME BASED ON PRODUCT RATE, HOUR A/M = FEED RATIO OF ACROLEIN TO MESH, MOLE RATIO PR = THE RATE OF PRODUCT MADE, G/MIN REC = PERCENT ACROLEIN RECOVERED PROM FEED, % YIELD = PERCENT FEED ACROLEIN CONVERTED TO ALDEHYDE PRODUCT, % CA = ACROLEIN CONC. IN LIQUID, WT. % CM = MESH CONC.IN LIQUID, WT. % |
Acetaldehyde | 0.11 wt. % |
Methyl Mercaptan | 0.88 |
Acrolein | 0.07 |
Allyl Alcohol | 0.29 |
Acetic Acid | 0.35 |
Acrylic Acid | 0.52 |
β-hydroxypropionaldehyde | 0.27 |
Pyridine | 0.19 |
MMP | 89.02 |
By-product having MW = 190 | 0.18 |
Water | 7.00 |
REACTOR SIZES AND OPERATING VARIABLES | |||||
REACTOR | TUBE SIZE | SEPARATOR | TEMP. | GAS RATE | LIQUID RATE |
Gas-lift | .5" id x 3.5' (or 5' w/spool) [1.27 cm id x 106.68 cm (or 152.40 cm w/spool] | 2.5" od x 8" [6.35 cm od x 20.32 cm] | 35-55 C | 2.2-4.0 l/m | 4.0-12 l/m |
Wetted Wall | .5" id x 4.5' [1.27 cm id x 137.16 cm] | 4" od x 6" [10.16 cm od x 15.24 cm] | 30-48 C | 3.0-6.5 l/m | .6-.8 l/m |
Horiz. Loop | .5" id x 7.5' [1.27 cm id x 228.60 cm] | 3" od x 11" [7.62 cm od x 27.94 cm] 4" od x 13" [10.16 cm od x 33.02 cm] | 37-40 C | 2.5-3.4 l/m | 9.5-13.3 l/m |
TYPICAL RESULTS OF REACTOR TESTED | |||
GAS LIFT | WETTED WALL | HORIZ. LOOP | |
Run No. | 041684 | 110184 | 011685 |
Inlet Gas Conc. Vol % acrol. | 16.0 | 16.8 | 17.3 |
Outlet Gas Conc. Vol % acrol. | 0.503 | 1.92 | 3.82 |
Reactor Temp., C | 41.0 | 36.0 | 40.0 |
Superficial Vel. | |||
Gas, f/s [m/s] | 1.304 [0.3975] | 1.46 [0.4450] | 1.39 [0.4237] |
Liq., f/s [m/s] | 3.5 [1.0668] | 0.3 [0.0914] | 5.7 [1.7374] |
Liquid Conc. | |||
Wt. % acrol. | 0.51 | 0.71 | 0.05 |
Wt % MeSH | 1.30 | 0.20 | 1.35 |
Gas Mixture Feed Rate. g/m | 4.43 | 4.84 | 4.56 |
Acrol. Feed Rate, g/m | 1.174 | 1.372 | 1.352 |
MeSH Vap. Feed Rate, g/m | 1.042 | 1.160 | 1.095 |
Aldehyde Product Rate, g/m | 2.267 | 2.306 | 2.118 |
Feed Recovery (acrol. + MeSH), wt. % | 94.2 | 88.2 | 82.1 |
Reactor Yield (ald./acr+MeSH, wt. % | 92.34 | 87.33 | 80.97 |
Ave. Mass Transfer Coeff., mol/l-atm-h | 150 | 120 | 50 |
Claims (6)
- A process for the continuous preparation of 3-[methylthio) propanal, comprising:contacting a gaseous acrolein feed stream with a liquid reaction medium in a gas/liquid contact zone, said reaction medium containing 3-(methylthio) propanal and a catalyst for the reaction between methyl mercaptan and acrolein, said gaseous acrolein feed stream comprising acrolein vapor and non-condensible gas, whereby acrolein from said feed stream is transferred to said liquid medium;introducing methyl mercaptan into said reaction medium in a proportion which is substantially stoichiometrically equivalent to the acrolein introduced into said medium, and reacting acrolein and methyl mercaptan in said liquid medium without substantial formation of the intermediate hemi(methylthio)acetal of 3-(methylthio) propanal to produce a liquid reaction product containing 3-(methylthio) propanal;dividing said reaction product into a product fraction and a circulating fraction; andrecycling said circulating fraction to said gas/liquid contact zone.
- A process according to claim 1, wherein the rate of said reaction is from three to ten times greater than the rate of the reaction would have been under otherwise the same conditions if the reaction were allowed to proceed through the intermediate hemi (methylthio)acetal.
- A process for the continuous preparation of 3-(methylthio) propanal, comprising:contacting a liquid reaction medium with a gaseous acrolein feed stream in a gas/liquid contact zone through which said feed stream and said reaction medium are passed countercurrently, said reaction medium containing 3-(methylthio) propanal and a catalyst for the reaction between methyl mercaptan and acrolein, said gaseous acrolein feed stream comprising acrolein vapor and non-condensible gas, whereby acrolein is transferred from said feed stream to said reaction medium;reacting acrolein with methyl mercaptan in said medium to produce a liquid reaction product containing 3-(methylthio) propanal, the liquid holdup in said countercurrent gas/liquid contact zone being sufficient so that the reaction between methyl mercaptan and acrolein proceeds substantially to completion within said zone;separating said non-condensible gas from said liquid reaction product;dividing said reaction product into fraction and a circulating fraction; andrecycling said circulating fraction to said gas/liquid contact zone.
- A process according to claim 3, wherein said gas/liquid contact zone comprises a tray column reactor.
- A process according to claim 3 or claim 4, wherein the total pressure in said gas/liquid contact zone is not greater than 2.03 bar (2 atmospheres).
- A process according to any one of claims 1 to 5, wherein said gaseous acrolein feed stream comprises not more than 8% by volume water vapor.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/073,763 US5352837A (en) | 1993-06-08 | 1993-06-08 | Process for the preparation of 3-(methylthio)propanal |
US73763 | 1993-06-08 | ||
EP93922171A EP0703890B1 (en) | 1993-06-08 | 1993-09-09 | Process for the preparation of 3-(methylthio)propanal |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93922171A Division EP0703890B1 (en) | 1993-06-08 | 1993-09-09 | Process for the preparation of 3-(methylthio)propanal |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0889029A2 true EP0889029A2 (en) | 1999-01-07 |
EP0889029A3 EP0889029A3 (en) | 2002-03-13 |
Family
ID=22115663
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98114518A Withdrawn EP0889029A3 (en) | 1993-06-08 | 1993-09-09 | Process for the preparation of 3- (methylthio) propanal |
EP93922171A Expired - Lifetime EP0703890B1 (en) | 1993-06-08 | 1993-09-09 | Process for the preparation of 3-(methylthio)propanal |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93922171A Expired - Lifetime EP0703890B1 (en) | 1993-06-08 | 1993-09-09 | Process for the preparation of 3-(methylthio)propanal |
Country Status (15)
Country | Link |
---|---|
US (1) | US5352837A (en) |
EP (2) | EP0889029A3 (en) |
JP (1) | JPH09501145A (en) |
KR (1) | KR100274685B1 (en) |
CN (1) | CN1041414C (en) |
AT (1) | ATE178594T1 (en) |
BR (1) | BR9307864A (en) |
DE (1) | DE69324380T2 (en) |
DK (1) | DK0703890T3 (en) |
ES (1) | ES2131120T3 (en) |
RU (1) | RU2118314C1 (en) |
SG (1) | SG43158A1 (en) |
TW (1) | TW270925B (en) |
WO (1) | WO1994029254A1 (en) |
ZA (1) | ZA935850B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8735631B2 (en) | 2008-11-20 | 2014-05-27 | Arkema France | Method for manufacturing methylmercaptopropionaldehyde and methionine using renewable raw materials |
Families Citing this family (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5905171A (en) * | 1995-06-22 | 1999-05-18 | Novus International, Inc. | Process for the preparation of 3-(methylthio)propanal |
US5637766A (en) * | 1993-06-08 | 1997-06-10 | Novus International, Inc. | Process for the preparation of 3-(methylthio) propanal |
US5925794A (en) * | 1993-06-08 | 1999-07-20 | Novus International, Inc. | Process for the preparation of 3-(methylthio)propanal |
EP0770062A4 (en) * | 1994-07-11 | 1999-02-10 | Novus Int Inc | Process for the preparation of 3-(methylthio)propanal |
WO1996040630A1 (en) * | 1995-06-07 | 1996-12-19 | Novus International, Inc. | Continuous hydrolysis process for preparing 2-hydroxy-4-methylthiobutanoic acid or salts thereof |
US5663409A (en) * | 1995-06-07 | 1997-09-02 | Novus International, Inc. | Process for the preparation of 3-(methylthio) propanal and 2-hydroxy-4-(methylthio) butanenitrile |
FR2735989B1 (en) * | 1995-06-29 | 1997-08-14 | Rhone Poulenc Nutrition Animal | PROCESS AND PLANT FOR PURIFYING A GAS FLOW CONTAINING ACROLEIN |
CN1042742C (en) * | 1995-11-02 | 1999-03-31 | 中国石化兰州炼油化工总厂 | Process for preparing lubricating oil additive |
US5825369A (en) * | 1996-01-16 | 1998-10-20 | International Business Machines Corporation | Compression of simple geometric models using spanning trees |
AU2594797A (en) * | 1996-04-01 | 1997-10-22 | Jonathan Lester Brockwell | Processes for the manufacture of methylmercaptopropanal |
US6166263A (en) * | 1997-03-27 | 2000-12-26 | Union Carbide Chemicals & Plastics Technology Corporation | Processes for the manufacture of acrolein |
US6187963B1 (en) | 1997-03-27 | 2001-02-13 | Union Carbide Chemicals & Plastics Technology Corporation | Processes for the manufacture of acrolein derivatives |
NL1007442C2 (en) * | 1997-11-04 | 1998-12-07 | Josephus Johannes Petrus Maria | Batch-Continuous counter-current equipment with superior performance. |
WO2001010776A1 (en) | 1999-08-05 | 2001-02-15 | Novus International, Inc. | Reductive combustion of ammonium salts of sulfuric acid |
FR2835831B1 (en) * | 2002-02-12 | 2006-09-01 | Aventis Animal Nutrition Sa | PROCESS FOR PURIFYING ACROLEIN |
JP4186572B2 (en) * | 2002-09-27 | 2008-11-26 | 住友化学株式会社 | Method for producing 3-methylthiopropanal |
DE102004038053A1 (en) | 2004-08-05 | 2006-04-27 | Degussa Ag | Process for the preparation of 3- (methylthio) propanal |
DE102005003990A1 (en) * | 2005-01-28 | 2006-08-03 | Degussa Ag | Preparation of 3-(alkylthio)propanal comprises reaction of glycerin or compounds obtained from glycerin, with a sulfur compound or compounds obtained from sulfur compound in the presence of a catalyst |
JP2010111642A (en) * | 2008-11-07 | 2010-05-20 | Sumitomo Chemical Co Ltd | Method for producing methionine |
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JP5402864B2 (en) | 2010-07-20 | 2014-01-29 | 住友化学株式会社 | Method for producing 3-methylthiopropanal |
DE102010064250A1 (en) * | 2010-12-28 | 2012-06-28 | Evonik Degussa Gmbh | Process for the preparation of methylmercaptopropionaldehyde |
EP2679579A1 (en) | 2012-06-27 | 2014-01-01 | Evonik Industries AG | Integrated method for producing acrolein and 3-Methylmercapto propionaldehyde |
EP3205643A1 (en) * | 2016-02-15 | 2017-08-16 | Evonik Degussa GmbH | Method for the preparation of 3-methylthiopropionaldehyde |
CN111116437B (en) * | 2018-11-01 | 2021-02-05 | 山东新和成氨基酸有限公司 | Method and apparatus for producing 2-hydroxy-4-methylthiobutyric acid and intermediate thereof |
WO2023118974A1 (en) * | 2021-12-24 | 2023-06-29 | Vinati Organics Limited | An agitator reactor for synthesis of acrylamido tertiary butyl sulfonic acid and process implemented thereon |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2626282A (en) * | 1949-10-05 | 1953-01-20 | Standard Oil Dev Co | Vapor phase production of betamethylmercaptopropionaldehyde |
US4225516A (en) * | 1975-06-20 | 1980-09-30 | Rhone-Poulenc Industries | Process for the manufacture of beta-methylthiopropionaldehyde |
US4319047A (en) * | 1979-07-10 | 1982-03-09 | Rhone-Poulenc Industries | Preparation of beta-methylthiopropionaldehyde |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA797873A (en) * | 1968-10-29 | Sumitomo Chemical Company | PROCESS FOR PRODUCING .beta.-METHYLMERCAPTOPROPIONALDEHYDE | |
CA820968A (en) * | 1969-08-19 | Shima Takesaburo | PROCESS FOR PRODUCING HIGH PURITY .beta.-METHYLMERCAPTOPROPIONALDEHYDE | |
US2542768A (en) * | 1945-10-24 | 1951-02-20 | Du Pont | Hydroxy-methylmercaptobutyronitrile |
US2564105A (en) * | 1949-08-03 | 1951-08-14 | Du Pont | Aqueous methionine nitrile sulfate |
US2676190A (en) * | 1951-10-23 | 1954-04-20 | Du Pont | Process for the manufacture of beta-methylmercapto-propionaldehyde |
US2776996A (en) * | 1955-12-22 | 1957-01-08 | Du Pont | Manufacture of beta-methylmercaptopropionaldehyde |
DE1618879B1 (en) * | 1966-04-18 | 1971-12-16 | Sumitomo Chemical Co | Process for the production of the purest beta-methyl mercaptopropionaldehyde |
BE697532A (en) * | 1966-04-25 | 1967-10-02 | ||
US3529940A (en) * | 1966-04-25 | 1970-09-22 | Sumitomo Chemical Co | Apparatus for two-stage production of beta-methylmercaptopropionaldehyde |
NL6706022A (en) * | 1966-04-30 | 1967-10-31 | ||
NL132124C (en) * | 1966-09-02 | |||
CH491882A (en) * | 1967-10-13 | 1970-06-15 | Glanzstoff Ag | Process for the preparation of B-methyl mercaptopropionaldehyde |
NL6809647A (en) * | 1968-07-09 | 1970-01-13 | ||
JPS49818B1 (en) * | 1970-08-12 | 1974-01-10 | ||
JPS4856144A (en) * | 1971-11-12 | 1973-08-07 | ||
BE791831A (en) * | 1971-11-26 | 1973-03-16 | Degussa | PROCESS FOR OBTAINING PURE 3-METHYLMERCAPTOPROPIONALDEHYDE |
DE2320544C2 (en) * | 1973-04-21 | 1975-06-05 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt | Process for the preparation of 3-methyl mercaptopropionaldehyde |
US5198578A (en) * | 1986-07-17 | 1993-03-30 | Union Carbide Chemicals | Anhydrous diluents for the propylene oxidation reaction to acrolein and acrolein oxidation to acrylic acid |
US5183936A (en) * | 1986-08-21 | 1993-02-02 | Union Carbide Chemicals & Plastics Technology Corporation | Anhydrous diluent process for the propylene oxidation reaction to acrolein and acrolein oxidation to acrylic acid |
US5155262A (en) * | 1988-09-26 | 1992-10-13 | Union Carbide Chemicals & Plastics Technology Corporation | Anhydrous diluents for the isobutylene oxidation reaction to methacrolein and methacrolein oxidation to methacrylic acid |
-
1993
- 1993-06-08 US US08/073,763 patent/US5352837A/en not_active Expired - Fee Related
- 1993-08-11 ZA ZA935850A patent/ZA935850B/en unknown
- 1993-09-09 DK DK93922171T patent/DK0703890T3/en active
- 1993-09-09 RU RU96100238/04A patent/RU2118314C1/en not_active IP Right Cessation
- 1993-09-09 JP JP7501709A patent/JPH09501145A/en not_active Ceased
- 1993-09-09 DE DE69324380T patent/DE69324380T2/en not_active Expired - Fee Related
- 1993-09-09 EP EP98114518A patent/EP0889029A3/en not_active Withdrawn
- 1993-09-09 AT AT93922171T patent/ATE178594T1/en active
- 1993-09-09 BR BR9307864A patent/BR9307864A/en not_active Application Discontinuation
- 1993-09-09 WO PCT/US1993/008552 patent/WO1994029254A1/en active IP Right Grant
- 1993-09-09 SG SG1996004573A patent/SG43158A1/en unknown
- 1993-09-09 KR KR1019950705025A patent/KR100274685B1/en not_active IP Right Cessation
- 1993-09-09 EP EP93922171A patent/EP0703890B1/en not_active Expired - Lifetime
- 1993-09-09 ES ES93922171T patent/ES2131120T3/en not_active Expired - Lifetime
- 1993-10-05 TW TW082108204A patent/TW270925B/zh active
- 1993-10-09 CN CN93118591A patent/CN1041414C/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2626282A (en) * | 1949-10-05 | 1953-01-20 | Standard Oil Dev Co | Vapor phase production of betamethylmercaptopropionaldehyde |
US4225516A (en) * | 1975-06-20 | 1980-09-30 | Rhone-Poulenc Industries | Process for the manufacture of beta-methylthiopropionaldehyde |
US4319047A (en) * | 1979-07-10 | 1982-03-09 | Rhone-Poulenc Industries | Preparation of beta-methylthiopropionaldehyde |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8735631B2 (en) | 2008-11-20 | 2014-05-27 | Arkema France | Method for manufacturing methylmercaptopropionaldehyde and methionine using renewable raw materials |
Also Published As
Publication number | Publication date |
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DE69324380D1 (en) | 1999-05-12 |
DK0703890T3 (en) | 1999-10-18 |
ES2131120T3 (en) | 1999-07-16 |
EP0703890A4 (en) | 1996-10-30 |
KR100274685B1 (en) | 2000-12-15 |
CN1096779A (en) | 1994-12-28 |
BR9307864A (en) | 1996-01-23 |
TW270925B (en) | 1996-02-21 |
SG43158A1 (en) | 1997-10-17 |
ZA935850B (en) | 1994-05-25 |
US5352837A (en) | 1994-10-04 |
JPH09501145A (en) | 1997-02-04 |
EP0889029A3 (en) | 2002-03-13 |
EP0703890A1 (en) | 1996-04-03 |
ATE178594T1 (en) | 1999-04-15 |
RU2118314C1 (en) | 1998-08-27 |
DE69324380T2 (en) | 1999-08-26 |
WO1994029254A1 (en) | 1994-12-22 |
AU673856B2 (en) | 1996-11-28 |
CN1041414C (en) | 1998-12-30 |
EP0703890B1 (en) | 1999-04-07 |
AU5126893A (en) | 1995-01-03 |
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